CN109496226B - Surface treatment composition capable of imparting underwater superoleophobic properties - Google Patents

Surface treatment composition capable of imparting underwater superoleophobic properties Download PDF

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Publication number
CN109496226B
CN109496226B CN201780046212.5A CN201780046212A CN109496226B CN 109496226 B CN109496226 B CN 109496226B CN 201780046212 A CN201780046212 A CN 201780046212A CN 109496226 B CN109496226 B CN 109496226B
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composition
group
core particle
groups
treatment composition
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CN109496226A (en
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S·达斯
D·马亨德兰
A·A·维迪雅
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Unilever IP Holdings BV
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    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
    • C09D5/16—Antifouling paints; Underwater paints
    • C09D5/1606—Antifouling paints; Underwater paints characterised by the anti-fouling agent
    • C09D5/1637—Macromolecular compounds
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
    • C09D5/16—Antifouling paints; Underwater paints
    • C09D5/1606—Antifouling paints; Underwater paints characterised by the anti-fouling agent
    • C09D5/1612—Non-macromolecular compounds
    • C09D5/1618—Non-macromolecular compounds inorganic

Abstract

The present invention relates to a surface treatment composition comprising functionalized micro/nanoparticles comprising a core particle having a diameter in the range of 50-5,000nm, said core particle carrying on its surface a plurality of covalently bound silane polymer residues, wherein said hydrophilic polymer residues are residues of a polymer selected from the group consisting of polyethylene glycol, polypropylene glycol, polyvinyl alcohol, polyacrylamide, polyoxazoline, polyethyleneimine, acrylic polymers, poly (vinyl pyrrolidone), polysaccharides, chitosan and copolymers thereof. The surface treatment composition is useful for imparting underwater superoleophobicity to a surface by treating the surface with the surface treatment composition. The invention also relates to the use of the above-mentioned surface treatment composition for imparting underwater superoleophobicity to a surface, for imparting soil resistance to a surface, and/or for imparting antimicrobial properties to a surface, said use comprising treating said surface with said treatment composition.

Description

Surface treatment composition capable of imparting underwater superoleophobic properties
Technical Field
The present invention relates to surface treatment compositions useful for imparting underwater superoleophobicity to surfaces by treating such surfaces with said surface treatment compositions. The surface treatment compositions of the present invention contain functionalized micro/nanoparticles that carry multiple covalently bonded silane polymer residues on the surface.
Disclosure of Invention
According to Young's equation, a liquid droplet in contact with a flat solid surface is contacted with the contact angle characteristics of the liquid and solid in question:
γSG–γSL–γLGcosθc＝0
wherein, γSG、γSLAnd gammaLGAre the surface tension of solid-gas, solid-liquid and liquid-gas, respectively, and θ is the contact angle of the droplet.
The solid-liquid interaction can be enhanced by using surface roughness. Increasing the surface area in contact with the droplet results in an expansion of the solid-liquid interaction, whereby the repellent surface becomes more repellent, or the liquid spreads further on the non-repellent surface. This assumes that the surface is fully wetted by the liquid and is referred to as the "Wenzel region". When considering droplets on a rough surface, another situation is where air pockets are trapped between the surface and the liquid, creating a composite interface called the " west-Baxter region". In this case, the surface generally becomes more repellent, since the droplets partly rest on the air pockets. Thus, the non-repelling surface may become repulsive through the increase in roughness and the formation of a composite air/solid interface.
The superoleophobic surface is advantageous for antifouling, self-cleaning, mud-resistant, low-drag, anti-fog, and oil-water separation applications. Current bio-excitation surface applications are limited due to lack of mechanical durability.
There are many examples of superoleophobic surfaces; these generally involve fluorinated components that provide low surface tension and roughness components that enhance liquid-solid interactions. Early examples were the use of a rough oxidized aluminum surface immersed in a fluorinated monoalkyl phosphate; resulting in a contact angle of oil and water of 150 deg.. Fluorinated polyhedral oligomeric silsesquioxanes have been used in a variety of contexts-including electrospinning and coating re-entry (coating re-entrant) structures-to produce superoleophobic coatings. However, superoleophobic surfaces have not proven to generally have good mechanical durability. Poor durability can be attributed to the commonly utilized "one-pot" technique, wherein the low surface tension materials required for oleophobicity are distributed throughout the coating, compromising adhesion to the substrate.
Superoleophobic composite surfaces are also typically superhydrophobic; because water has a higher surface tension, oil-repellent surfaces generally also repel water.
Ghosh et al (Surface Chemical Modification of Poly (dimethyliloxane) -Based biomedical Materials: Oil-repeat Surfaces; applied. Mater. interfaces (2009),1(11),2636-2644) describe experiments Based on PolyThe oil repellency properties of the biomimetic replica (PDMS-replica) of (dimethylsiloxane) were tuned by changing its surface chemical composition. Preparation of mixed-CF with graded roughness in the presence of surface modifiers using soft lithography-based nano-casting3and-SiCH3PDMS-replica of the complementary combination of end functional groups. The PDMS replica showed superhydrophobicity and enhanced oil repellency, θOil86 deg.. The PDMS-replica was further modified with silica nanoparticles followed by chemical vapor deposition of (heptadecafluoro-1, 1,2, 2-tetrahydrodecyl) trichlorosilane. -CF3End-capped silica-modified PDMS-replica (i.e., PDMS-replica silica/CF3) Exhibit both superhydrophobicity and high oil repellency (advancing theta)Oil～120°)。
Ghosh et al (Water-Based Layer-by-Layer Surface Chemical Modification of biomedical Materials: Oil reproduction; applied. Mater. interfaces (2013),5 (18); 8869-8874) report Chemical Modification of the Surface of Biomimetic Materials by Water-Based Layer-by-Layer deposition. Preparation of amine terminated biomimetic replica PDMS-replica silica/NH by treating a silica modified replica (i.e. PDMS-replica silica) with an aqueous solution of branched Ethoxylated Polyethyleneimine (EPEI)2. Next, PDMS-replica silica/NH was treated by an aqueous solution of phosphate fluorosurfactant2obtaining-CF3End PDMS-replica silica/NH2/CF3. PDMS-replica silica/NH2/CF3Shows super-hydrophobicity (advancing theta)Water (W)140 deg.) and high oil repellency (advance theta)Oil110 °). X-ray photoelectron spectroscopy (XPS) showed the presence of silica/NH in PDMS-replica2/CF3Well organized terminal-CF on surfaces3A group.
The above oil repellent surface has the following disadvantages: when placed under water, they tend to attract oily or hydrophobic stains.
US 2008/0177022 describes a hydrophilic film-forming composition comprising:
an oxyalkylene compound containing at least 2 hydroxyl groups in its molecule;
alkoxide compound containing an element selected from Si, Ti, Zr, and Al; and
a hydrophilic polymer comprising a silane coupling group at the polymer end.
US 2010/0159256 describes a composition for forming a hydrophilic membrane, the composition comprising:
a hydrophilic polymer having a silane coupling group at a terminal or a side chain of the polymer; and
a metal complex catalyst.
US 2011/0024292A 1(Armstrong et al) discloses a composition suitable for chromatography. The compositions disclosed in this document comprise a solid carrier and/or a polymer comprising a derivatized cyclofructan (cyclofructan) compound. There is no disclosure of compounds/compositions that can impart superoleophobic characteristics, nor of compositions containing silanes coupled to selected polymers.
US 2013296453 AA (Ciba) discloses functionalized SiO2、Al2O3Or mixed SiO2And Al2O3A nanoparticle comprising a covalently bound group that is a group of a silane on a surface. These functionalized nanoparticles can be used as stabilizers and/or compatibilizers in organic materials, or as photoinitiators in pre-polymerization or pre-crosslinking formulations, or as coating enhancers and anti-scratch modifiers in coating compositions for surfaces. There is no disclosure of compounds/compositions that can impart superoleophobic characteristics, nor of compositions containing silanes coupled to selected polymers as claimed in this application.
US 20110084421 a1(Soan Labs) discloses a plurality of particles configured to impart a surface texture, and an ultralyophobic-inducing composition attached to the plurality of particles, the ultralyophobic-inducing composition comprising at least one polyamine segment and a plurality of branch segments attached to the at least one polyamine segment, the plurality of branch segments comprising at least one of a hydrophobic segment and an oleophobic segment. The branched segments of the coating composition may be covalently bonded to the at least one polyamine segment, or they may not be covalently bonded to the at least one polyamine segment. The ultralyophobic-inducing composition may be attached to the plurality of particles using a multifunctional coupling agent. The multifunctional agent may comprise a functional group including an epoxy, a hydroxyl, an alkoxy, or a halogen. The polyfunctional coupling agent may include a silane coupling agent. In embodiments, the ultralyophobic-inducing composition may directly contact the surface of the plurality of particles. In embodiments, at least one polyamine segment of the ultralyophobic-inducing composition comprises chitosan.
Disclosure of Invention
The present inventors have developed a surface treatment composition that can be used to impart underwater superoleophobicity to a surface by treating such surface with the surface treatment composition.
The surface treatment composition of the present invention contains functionalized micro/nanoparticles comprising a core particle having a diameter in the range of 50-5,000nm, the core particle carrying a plurality of covalently bound silane polymer residues on the surface. These covalently bound silane polymer residues are represented by formula (I):
(-O)a(R1O)b(R2)3-a-bSi-R3-X-pol (I)
wherein:
R1and R2Each independently selected from a hydrogen atom and optionally substituted C1-20An alkyl group;
R3selected from substituted and unsubstituted C1-12An alkylene group;
x is selected from NR4O, S or P, wherein R4Represents a hydrogen atom or C1-3An alkyl group;
pol is a hydrophilic polymer residue;
a is 1,2 or 3;
b is 0, 1 or 2; and is
a+b≤3
Wherein the hydrophilic polymer residue is a residue of a polymer selected from the group consisting of polyethylene glycol, polypropylene glycol, polyvinyl alcohol, polyacrylamide, polyoxazoline, polyethyleneimine, acrylic polymers, poly (vinyl pyrrolidone), polysaccharides, chitosan, and copolymers thereof.
When the surface treatment composition of the present invention is used to treat a surface, such as enamel, the functionalized micro/nanoparticles attach themselves to the surface, thereby creating a deposited layer of functionalized micro/nanoparticles. This deposited layer on the treated surface imparts underwater superoleophobicity to the surface. Thus, the treated surface is effective to repel hydrophobic stains when placed under water.
The invention also relates to the use of the above-mentioned surface treatment composition for imparting underwater superoleophobicity to a surface, for imparting soil resistance to a surface, and/or for imparting antimicrobial properties to a surface, said use comprising treating said surface with said treatment composition.
In addition, the present invention provides a method for preparing the above functionalized micro/nanoparticles.
Detailed Description
A first aspect of the present invention relates to a surface treatment composition capable of imparting underwater superoleophobicity to a surface, the surface treatment composition containing a functionalized micro/nanoparticle comprising a core particle having a diameter in the range of 50-5,000nm, the core particle carrying a plurality of covalently bonded silane polymer residues on the surface, wherein the covalently bonded silane polymer residues are represented by formula (I):
(-O)a(R1O)b(R2)3-a-bSi-R3-X-pol (I)
wherein:
R1and R2Each independently selected from a hydrogen atom and optionally substituted C1-20An alkyl group;
R3selected from substituted and unsubstituted C1-12An alkylene group;
x is selected from NR4O, S or P, wherein R4Represents a hydrogen atom or C1-3An alkyl group;
pol is a hydrophilic polymer residue;
a is 1,2 or 3;
b is 0, 1 or 2; and is
a+b≤3
Wherein the hydrophilic polymer residue is a residue of a polymer selected from the group consisting of polyethylene glycol, polypropylene glycol, polyvinyl alcohol, polyacrylamide, polyoxazoline, polyethyleneimine, acrylic polymers, poly (vinyl pyrrolidone), polysaccharides, chitosan, and copolymers thereof.
The term "diameter" as used herein in relation to particles refers to the average equivalent spherical diameter of the particles, unless otherwise specified. The particle size distribution of a particular material can be determined, for example, by means of laser diffraction. Care should be taken to separate loose particle aggregates prior to particle size measurement. Particle size can be measured using SEM or dynamic light scattering or a commercially available particle size analyzer from, for example, Malvern or Brookhaven.
The hydrophilic polymer residue on the surface of the functionalized micro/nanoparticles is a residue of a polymer selected from the group consisting of polyethylene glycol, polypropylene glycol, polyvinyl alcohol, polyacrylamide, polyoxazoline, polyethyleneimine, acrylic polymers, poly (vinyl pyrrolidone), polysaccharides, chitosan, and copolymers thereof. More preferably, the hydrophilic polymer residue is a residue of a polymer selected from the group consisting of polyethylene glycol, polypropylene glycol and copolymers thereof. Most preferably, the polymer residue is a polyethylene glycol residue.
Typically, the degree of polymerization of the hydrophilic polymer residues is greater than 3(n >3), more preferably greater than 10(n >10), and most preferably greater than 20(n > 20); "n" is the number of monomer units.
R in the formula (I)1Preferably selected from hydrogen atoms and optionally substituted C1-5An alkyl group. More preferably, R1Selected from the group consisting of hydrogen atom, methyl group, ethyl group, n-propyl group and isopropyl group. Most preferably, R1Selected from the group consisting of hydrogen atoms, methyl groups and ethyl groups.
R in the formula (I)2Preferably selected from hydrogen atoms and optionally substituted C1-5An alkyl group. More preferably, R2Selected from the group consisting of hydrogen atom, methyl group, ethyl group, n-propyl group and isopropyl group. Most preferably, R2Selected from the group consisting of hydrogen atoms, methyl groups and ethyl groups.
Preferably, R in formula (i)3Selected from substituted and unsubstituted C1-5Alkylene, more preferablyIs selected from unsubstituted C1-5Alkylene, most preferably selected from unsubstituted C2-4An alkylene group. X in the formula (I) preferably represents NR4Or O. More preferably, X represents NR4Wherein R is4Represents a hydrogen atom or C1-3An alkyl group. Most preferably, X represents NH.
In another preferred embodiment, the integers a and b in formula (I) satisfy the condition: a + b is more than or equal to 2. Most preferably, a + b is 3.
The core particle in the functionalized micro/nanoparticles may be made of inorganic and/or organic materials. Preferably, the core particle is made of an inorganic material. More preferably, the core particle is made of silica, calcium carbonate, zinc oxide, titanium dioxide, hydrotalcite or hydroxyapatite. Even more preferably, the core particle is made of silica or hydroxyapatite. Most preferably, the core particle is made of silica.
The diameter of the core particle is preferably in the range of 100 to 5000nm, more preferably in the range of 150 to 4000nm and most preferably in the range of 200 to 2000 nm.
According to a particularly preferred embodiment, at least 50% of the surface of the core particle of the functionalized micro/nanoparticles is covered by covalently bound silane polymer residues.
The surface treatment composition of the present invention may be provided in various forms (e.g., paste, gel, liquid or powder). Preferably, the surface treatment composition is in the form of a paste, gel or liquid. More preferably, the surface treatment composition is in the form of a paste or gel. Most preferably, the composition is in the form of a paste.
The surface treatment composition typically contains 0.1 wt.% to 45 wt.% functionalized micro/nanoparticles. More preferably, the composition contains 0.5 to 40 wt.%, even more preferably 1 to 30 wt.%, and most preferably 5 to 20 wt.% functionalized micro/nanoparticles.
According to a particularly preferred embodiment, the functionalized micro/nanoparticles are homogeneously dispersed throughout the surface treatment composition. To ensure that the functionalized micro/nanoparticles remain suspended in the liquid-based formulation, gelling agents, structuring agents, and viscosity-increasing agents may be suitably employed.
Examples of surface treatment compositions of the present invention encompass toothpastes, tooth powders, mouthwashes, hard surface cleaning compositions, toilet bowl cleaning compositions and household cleaning compositions. According to a preferred embodiment, the surface treatment composition is a toothpaste, a tooth powder or a mouthwash. Most preferably, the surface treatment composition is a toothpaste.
In addition to the functionalized micro/nanoparticles, the toothpaste may suitably contain one or more further ingredients selected from: abrasive (e.g., aluminum hydroxide (Al (OH))3) Calcium carbonate (CaCO)3) Various calcium hydrogenphosphates, various silicas and zeolites, and hydroxyapatite (Ca)5(PO4)3Particles of OH)), fluorides (e.g. NaF, SnF)2、Na2PO3F) Surfactants (e.g. sodium lauryl sulfate), antibacterial agents (ZnCl)2) A flavorant (e.g., peppermint, spearmint, or wintergreen), and a remineralizing agent (hydroxyapatite nanocrystals and calcium phosphate). Preferably, the toothpaste contains at least two, more preferably at least three and most preferably at least four of the above ingredients.
Another aspect of the present invention relates to a method of preparing functionalized micro/nanoparticles as defined herein, said method comprising:
providing core particles having a diameter in the range of 50-5,000 nm; and
covalently bonding a reactive hydrophilic polymer to the core particle by means of a silane coupling agent to produce a core particle carrying a plurality of covalently bonded silane polymer residues on the surface.
The core particles may be made of inorganic and/or organic materials. Preferably, the core particle is made of an inorganic material. More preferably, the core particle is made of silica, calcium carbonate, zinc oxide, titanium dioxide, hydrotalcite or hydroxyapatite. Even more preferably, the core particle is made of silica or hydroxyapatite. Most preferably, the core particle is made of silica.
The diameter of the core particle is preferably in the range of 100 to 5000nm, more preferably in the range of 150 to 4000nm and most preferably in the range of 200 to 2000 nm.
In the present method, it is preferred that at least 50% of the surface of the core particle is covered by covalently bound silane polymer residues.
In the present method, a reactive hydrophilic polymer is covalently attached to the surface of a core particle using a silane coupling agent. To this end, the silane coupling agent contains at least one reactive group capable of reacting with the reactive group on the surface of the core particle under formation of a covalent bond. In addition, the silane coupling agent contains at least one other reactive group capable of reacting with the reactive group in the hydrophilic polymer under the formation of a covalent bond.
According to a particularly preferred embodiment, the silane coupling agent used in the present process is represented by the following formula (II):
(R1O)i(R2)3-iSi-R3-Y (II)
wherein:
R1、R2and R3Have the meaning as defined hereinbefore;
y is a reactive group selected from vinyl, alkenyl, epoxy, amine, and mercapto; and is
i is 1,2 or 3.
Residue R in formula (II)1The O-is capable of reacting with reactive groups on the surface of the core particle. Examples of such reactive groups include hydroxyl (SiOH and-CHOH, CH)2OH) and a silicon hydride group (-SiH).
The reactive group Y in formula (II) is capable of reacting with the reactive group in the reactive hydrophilic polymer. Preferably, the reactive group Y in formula (II) is selected from epoxy and amine groups. More preferably, the reactive group Y is an amine group, most preferably a primary amine group.
The reactive hydrophilic polymer used in the present process preferably contains one or more reactive groups selected from the group consisting of hydroxyl groups, epoxy groups, thiol groups, vinyl groups and chlorohydroxy groups, more preferably, the reactive hydrophilic polymer contains one or more reactive groups selected from the group consisting of thiol groups, epoxy groups and amine groups. Most preferably, the reactive hydrophilic polymer contains reactive groups in the form of epoxy residues.
According to a particularly preferred embodiment, the reactive groups of the reactive hydrophilic polymer are terminal groups, such as terminal epoxy groups.
In one embodiment of the method, the reactive hydrophilic polymer is covalently bound to the core particle by first covalently binding the silane coupling agent to the surface of the core particle, followed by covalently binding the reactive hydrophilic polymer to the surface binding residues of the silane coupling agent. According to this embodiment, the method comprises the steps of:
pretreating the core particle with a first solution containing a silane coupling agent and reacting a reactive group on the surface of the core particle with the silane coupling agent to covalently bond the silane coupling agent to the surface of the core particle; and
the pretreated core particle is treated with a second solution containing a reactive hydrophilic polymer to covalently bond the hydrophilic polymer to the silane coupling agent residue on the surface of the core particle.
In an alternative embodiment of the method, the reactive hydrophilic polymer and the silane coupling agent are first reacted to produce the reactive silane polymer conjugate, and subsequently, the reactive silane polymer conjugate is covalently bound to the core particle. According to this embodiment, the method comprises the steps of:
preparing a reactive silane polymer conjugate by reacting a reactive hydrophilic polymer with a silane coupling agent;
treating the core particle with a solution containing a reactive silane polymer conjugate to covalently bind the conjugate to the surface of the core particle.
Pretreating the core particle with a first solution containing a silane coupling agent and reacting the reactive group on the surface of the core particle with the silane coupling agent to covalently bond the silane coupling agent to the surface of the core particle; and
treating the pretreated core particle with a second solution containing a reactive hydrophilic polymer to covalently bond the hydrophilic polymer to the silane coupling agent residue on the surface of the core particle.
Yet another aspect of the invention relates to the use of a surface treatment composition of the invention for imparting superoleophobicity to water, for imparting soil resistance to a surface, and/or for imparting antimicrobial properties to a surface, said use comprising treating said surface with said surface treatment composition.
According to a particularly preferred embodiment, the surface to be treated with the surface treatment composition consists predominantly (>50 wt.%) of apatite, ceramic, marble or metal. More preferably, the surface is made of apatite, ceramic or marble. Even more preferably, the surface consists of apatite, most preferably hydroxyapatite. Hydroxyapatite is the major component of dental enamel.
A particularly preferred embodiment of the use of the present invention comprises applying the surface treatment composition to the teeth of a human, most preferably using a toothbrush.
According to another particularly preferred embodiment, the surface treated with the surface treatment composition of the present invention is subjected to a surface roughening treatment prior to treatment with the surface treatment composition. The present inventors have found that such a pretreatment can significantly enhance the effectiveness of treatment with the surface treatment composition. Etching is an example of a surface roughening treatment that can be suitably employed according to the present invention. In case the surface to be treated is enamel, preferably dental etching techniques known in the art are applied prior to treatment with the surface treatment composition.
The use of the present invention preferably results in a treated surface having an underwater oil contact angle of greater than 80 degrees, more preferably 90-155 degrees, most preferably 110-150 degrees.
The underwater interface energy of the treated surface obtained according to the present use is generally from 10 to 35 dynes/cm. More preferably, the underwater interface energy of the treated surface is from 20 to 30 dynes/cm, most preferably from 22 to 28 dynes/cm.
The invention is further illustrated by the following non-limiting examples.
Examples
Example 1
Surface roughened PDMS replica films were prepared as reported by Ghosh et al (Surface Chemical Modification of Poly (dimethyliloxane) -Based biomedical Materials: Oil-repeat Surfaces; applied. Mater. interfaces (2009),1(11), 2636-2644). The PDMS membrane was treated with an oxidizing mixture of hydrochloric acid (35%, 4mL), hydrogen peroxide (30%, 4mL) and water (8mL) for 10 minutes. Next, the oxidized PDMS film was rinsed with distilled water and purged with nitrogen. The dried oxidized PDMS film was immediately immersed in the sol-gel mixture with the patterned surface facing the solution.
Silica nanoparticles (spherical, volume weighted average particle size 160nm) were deposited onto the oxidized PDMS film. After drying, the silica-modified PDMS film was treated with 5% (w/v) (3-aminopropyl) trimethoxysilane (97% pure from Aldrich) in methanol solution. Subsequently, the amine-functionalized PDMS membrane was treated with an epoxy-functionalized polyglycol to create a superoleophobic surface.
Epoxy-functional polyglycols have been synthesized beforehand as follows:
5.0g of polyalkylene glycol monoallyl ether [ CH ]2＝CHCH2(OCH2CH2)n(OCH2CH(CH3))mOH](1 eq) (where n ═ 19, m ═ 5) was dissolved in 90mL of toluene placed in a 100mL two neck dry round bottom flask attached to a Dean Stark apparatus attached to a water condenser. Nitrogen was continuously purged into the reaction mixture using a Schlenk line. The reaction mixture was stirred at 140 ℃ for 3 h. After the reaction mixture was completely dried, the temperature of the system was lowered to 25 ℃. 0.639g (1.5 eq) of 3-chloroperoxybenzoic acid (MCPBA) was then added to the reaction mixture and stirred at 25 ℃ for about 60 h. The progress of the epoxidation reaction was monitored using thin layer chromatography. After completion of the reaction, the solvent was evaporated using a rotary evaporator, and a yellow viscous liquid was obtained. 5% NaHCO was used3The product was purified in aqueous solution. The organic layer was washed with a hexane-ethyl acetate (12:7v/v ratio) solvent mixture. After it was treated with sodium sulfate, the solvent was evaporated under vacuum and a colorless viscous liquid was obtained.
The underwater static oil contact angles of the untreated PDMS membrane and the superoleophobic PDMS membrane were measured using a captive bubble technique (and light liquid paraffin oil). The results are shown in Table 1.
TABLE 1
Underwater oil contact angle
Untreated PDMS membranes 20°
Super oleophobic PDMS membrane 145°

Claims (15)

1. A surface treatment composition capable of imparting underwater superoleophobicity to a surface, the composition comprising a functionalized micro/nanoparticle comprising a core particle having a diameter in the range of 50-5,000nm, the core particle carrying a plurality of covalently bonded silane polymer residues on the surface, wherein the covalently bonded silane polymer residues are represented by formula (I):
(-O)a(R1O)b(R2)3-a-bSi-R3-X-pol (I)
wherein:
R1and R2Each independently selected from a hydrogen atom and optionally substituted C1-20An alkyl group;
R3selected from substituted and unsubstituted C1-12An alkylene group;
x is selected from NR4O, S or P, wherein R4Represents a hydrogen atom or C1-3An alkyl group;
pol is a hydrophilic polymer residue;
a is 1,2 or 3;
b is 0, 1 or 2; and is
a+b≤3
Wherein the hydrophilic polymer residue is a residue of a polymer selected from the group consisting of polyethylene glycol, polypropylene glycol and copolymers thereof;
wherein the composition contains 0.1 to 45 wt.% of the functionalized micro/nanoparticles; and
wherein the composition is a hard surface cleaning composition.
2. The composition of claim 1, wherein the hard surface cleaning composition is a toilet bowl cleaning composition.
3. The composition of claim 1, wherein the composition is a household cleaning composition.
4. The composition of claim 1, wherein the composition is a toothpaste, a tooth powder, or a mouthwash.
5. The composition according to any one of claims 1 to 4, wherein the core particle is made of silica, calcium carbonate, zinc oxide, titanium dioxide, hydrotalcite or hydroxyapatite.
6. The composition of any one of claims 1 to 4, wherein the composition is a paste, gel, liquid, or powder.
7. The composition of any one of claims 1 to 4, wherein the functionalized micro/nanoparticles are uniformly dispersed throughout the composition.
8. The composition of claim 7, wherein the composition is a toothpaste.
9. The composition of any one of claims 1 to 4, wherein the functionalized micro/nanoparticles are prepared using a method comprising:
providing core particles having a diameter in the range of 50-5,000 nm; and
covalently bonding a reactive hydrophilic polymer to the core particle with the aid of a silane coupling agent to produce a core particle carrying a plurality of covalently bonded silane polymer residues on the surface.
10. The composition of claim 9, wherein the reactive hydrophilic polymer contains one or more reactive groups selected from the group consisting of hydroxyl groups, epoxy groups, thiol groups, vinyl groups, and chlorohydroxy groups.
11. The composition of claim 10, wherein the reactive group is an epoxy group.
12. The composition of claim 9, wherein the silane coupling agent is represented by the following formula (II):
(R1O)i(R2)3-iSi-R3-Y (II)
wherein:
R1、R2and R3Has the same meaning as in claim 1;
y is a reactive group selected from vinyl, alkenyl, epoxy, amine, and mercapto; and is
i is 1,2 or 3.
13. The composition of claim 12, wherein the reactive group Y is an amine group.
14. The composition of claim 13, wherein the amine groups are primary amine groups.
15. Use of a surface treatment composition according to any preceding claim for imparting underwater superoleophobicity to a surface, for imparting soil resistance to a surface, and/or for imparting antimicrobial properties to a surface, the use comprising treating the surface with the surface treatment composition.
CN201780046212.5A 2016-07-26 2017-07-03 Surface treatment composition capable of imparting underwater superoleophobic properties Expired - Fee Related CN109496226B (en)

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